Contemporary Catalysis: Science, Technology, and Applications - Hardcover

Hardcover

ISBN 10: 1849739900 ISBN 13: 9781849739900

Publisher: Royal Society of Chemistry, 2017

Synopsis

Encompassing an integrated approach to the various aspects of catalysis, covering heterogeneous, homogeneous, organo-, bio-, and computational catalysis, as well as reaction and reactor engineering on an advanced level, this textbook is ideal for graduate students with diverse backgrounds, including catalysis, engineering, and organic synthesis. The basic principles of the various fields of catalysis are introduced in a concise way, preparing the reader for the more advanced chapters. Organometallic chemistry, surface science, biochemistry, nanoscience, transport phenomena and kinetics, reactor and reaction engineering are presented, spanning from the underlying science to industrial applications. Several important case studies on industrial applications are given. It includes catalyst preparation and characterisation and explores recent developments in the understanding of catalytic mechanisms, exploring advanced techniques such as operando spectroscopy.

About this title

About the Authors

Paul C J Kamer is a Professor at the University of St Andrews, Scotland. His research focuses on homogeneous catalysis with an emphasis on the synthesis of phosphorus donor ligands by rational design assisted by molecular modelling.

Dieter Vogt is a Professor at the University of Edinburgh. Scotland. His research interests cover homogeneous catalysis, catalyst recycling, mechanistic studies, ligand design and sustainable chemistry.

Joris Thybaut is a Professor at Ghent University, Belgium. His research interests are in catalytic reaction engineering with a focus on kinetics and reactors.

From the Back Cover

Encompassing an integrated approach to the various aspects of catalysis, covering heterogeneous, homogeneous, organo-, bio-, and computational catalysis, as well as reaction and reactor engineering on an advanced level, this textbook is ideal for graduate students with diverse backgrounds, including catalysis, engineering, and organic synthesis.

The basic principles of the various fields of catalysis are introduced in a concise way, preparing the reader for the more advanced chapters. Organometallic chemistry, surface science, biochemistry, nanoscience, transport phenomena and kinetics, reactor and reaction engineering are presented, spanning from the underlying science to industrial applications. Several important case studies on industrial applications are given. It includes catalyst preparation and characterisation and explores recent developments in the understanding of catalytic mechanisms, exploring advanced techniques such as operando spectroscopy.

From the Inside Flap

Encompassing an integrated approach to the various aspects of catalysis, covering heterogeneous, homogeneous, organo-, bio-, and computational catalysis, as well as reaction and reactor engineering on an advanced level, this textbook is ideal for graduate students with diverse backgrounds, including catalysis, engineering, and organic synthesis.

The basic principles of the various fields of catalysis are introduced in a concise way, preparing the reader for the more advanced chapters. Organometallic chemistry, surface science, biochemistry, nanoscience, transport phenomena and kinetics, reactor and reaction engineering are presented, spanning from the underlying science to industrial applications. Several important case studies on industrial applications are given. It includes catalyst preparation and characterisation and explores recent developments in the understanding of catalytic mechanisms, exploring advanced techniques such as operando spectroscopy.

Excerpt. © Reprinted by permission. All rights reserved.

Contemporary Catalysis

Science, Technology, and Applications

By Paul C. J. Kamer, Dieter Vogt, Joris W. Thybaut

The Royal Society of Chemistry

Copyright © 2017 The Royal Society of Chemistry
All rights reserved.

ISBN: 978-1-84973-990-0

Contents

Section I Introduction, 
1 History of Catalysis Jacob A. Moulijn and Rutger A. van Santen, 
2 Feedstocks and Renewable Resources Johannes G. de Vries, Peter J. Deuss and Katalin Barta, 
3 Current Challenges in Catalysis Dieter Vogt and Nicholas J. Westwood, 
Section II Underlying Principles for Catalysis, 
4 Organometallic Chemistry and Elementary Steps Piet W. N. M. van Leeuwen, 
5 Nanoscience Christopher J. Baddeley, 
6 An Introduction to Biocatalysis R. Wever, R. J. M. Goss, E. Spence, Xiaoxue Tong and A. F. Hartog, 
7 Thermodynamics and Kinetics Nicole Wilde and Roger Gläser, 
Section III Fundamental Catalysis, 
8 Heterogeneous Catalysis Harry Bitter, 
9 Homogeneous Catalysis Dieter Vogt, 
10 Organocatalysis Daniel G. Stark and Andrew D. Smith, 
11 Biocatalysis R. Wever, M. J. Corr, R. J. M. Goss and Paul Kamer, 
12 Computational Catalysis Stuart A. Macgregor, Michael Bühl and Emiel J. M. Hensen, 
13 Introduction to Electrocatalysis John T. S. Irvine, 
14 Photocatalysis Akihiko Kudo, 
Section IV Catalyst Preparation, 
15 Solid Materials for Heterogeneous Catalysis Nicole Wilde and Roger Gläser, 
16 Transition Metal Complexes and Ligand Synthesis David J. Nelson and Steven P. Nolan, 
17 Organocatalysts Aileen B. Frost, Mark D. Greenhalgh and Andrew D. Smith, 
18 Enzymes for Biocatalysis: Key Concepts, Engineering Principles and Case Studies Guiomar Sánchez-Carrón and Dominic J. Campopiano, 
Section V Catalyst Characterization, 
19 Advanced Solution Spectroscopic Techniques Jonathan A. Iggo and Alice Parry, 
20 X-Ray Photoelectron Spectroscopy Adam F. Lee, Christopher M. A. Parlett and Karen Wilson, 
21 Bulk X-Ray Techniques Adam F. Lee, Christopher M. A. Parlett and Karen Wilson, 
22 Adsorption Methods Adam F. Lee, Christopher M. A. Parlett and Karen Wilson, 
23 Temperature Programmed Techniques Adam F. Lee, Christopher M. A. Parlett and Karen Wilson, 
Section VI Operando Techniques, 
24 Operando Techniques M. Bauer, U. Bentrup, J. B. Priebe and A. Brückner, 
Section VII Reaction and Reactor Engineering, 
25 Reaction and Reactor Engineering Jeroen Lauwaert, Joris W. Thybaut, Alexandre Goguet, Christopher Hardacre, Oluwafunmilola Ola and Mercedes Maroto-Valer, 
Section VIII Separation, 
26 Catalyst Separation Robert Konrath, Frank J. L. Heutz, Paul C. J. Kamer and Dieter Vogt, 
Section IX Process Intensification, 
27 Process Intensification in Catalysis Sebastian Falß, Martin Rieks and Norbert Kockmann, 
Section X Industrial Processes, 
28 Transition Metal Catalysed Methanol Carbonylation Anthony Haynes, 
Section XI Life Cycle Analysis, 
29 Environmental Analyses and Life Cycle Assessment Studies Dana Kralisch and Denise Ott, 
Subject Index, 

CHAPTER 1

History of Catalysis

Jacob A. Moulijn and Rutger A. van Santen,

1.1 History of Catalysis – Introduction

Without catalysis, life is not possible and, in that sense, catalysis is as old as life. The oldest catalytic processes used by humans are the production of wine, beer, alcohol and acetic acid, all through the fermentation of carbohydrates. This technology was already practised earlier than 2000 years BC. Compared to biocatalysts, the utilisation of chemocatalysts in industrial production is recent. Over the years, catalysis has developed into a broad discipline. History includes a wealth of theories and achievements that have changed society. Since catalysis as a whole is a topic too broad, we will not try to completely cover all historic developments. We will mention the numerous successful multicomponent catalyst systems as a chronological list presented in a table. In this chapter, the history of catalysis will be presented with a flavour of practical applications and a focus on heterogeneous (chemo)catalysis.

The name 'catalysis' was coined by Berzelius in 1836. He concluded that besides 'affinity', a new force was operative, a 'Catalytic Force'. The word 'catalysis' stems from the Greek: ?ata??s?, which means loosening, allow to move downwards freely. In the time of Berzelius, the term 'affinity' was used; however, on a molecular level, no understanding existed of reaction rates. Although insight was limited, catalysis as a new tool was booming.

When we limit ourselves to catalytic production processes of chemicals, the first commercial application was the production of sulphuric acid in the mid-18th century. The history of the production of sulphuric acid is interesting. In the Middle Ages, it was synthesised in the laboratory in glass equipment by burning sulphur with nitric acid in humid air. In 1746, lead was introduced as a construction material and the so-called lead chamber process allowed commercial production. In 1793, Clément and Desormes discovered that the quantity of nitric acid could be reduced if additional air was provided: a catalytic process was born. They realised that SO2 was converted into SO3 by air and that nitrous vapours were not consumed in a stoichiometric reaction but they were only intermediates. Remarkably, this process was a homogeneously catalysed process: in aqueous solution, SO2 is oxidised to sulphuric acid with nitrogen oxides functioning as O-transfer agents. A specific characteristic of the process is that, at high sulphuric acid concentrations, stable nitrosyl sulfate compounds are formed making it impossible to produce sulphuric acid in high concentration and purity. As early as 1831, a process was patented in which the oxidation was catalysed by a solid catalyst, Pt, allowing the production of the generally desired concentrated sulphuric acid. A commercial application, however, was strongly delayed due to practical difficulties, the major one being the low stability of the catalyst. It should be noted that elemental sulphur was initially the raw material. Later, pyrite was used because of its lower price. However, processing of pyrite ore was associated with considerable amounts of impurities, which acted as catalyst poisons. Not surprisingly, the Pt crystals were more sensitive to poisons than nitrogen oxides. This is a major reason why it took so long before a heterogeneously catalysed process became feasible. Nowadays, all processes for the production of sulphuric acid are heterogeneous. Vanadium-based catalysts have largely replaced Pt catalysts as they are cheaper and less susceptible to poisoning. Vanadium is present as a liquid salt in the pores of a porous solid carrier. At present, the raw material for the production of sulphuric acid is mainly elemental sulphur again, strongly reducing the catalyst deactivation. Sulphur is not expensive as it is a by-product from the hydrotreatment of oil fractions.

Around the turn of the 18th century, the influence of metal and metal oxides on decomposition reactions was a hot topic. An example is the decomposition of ethanol. In the presence of copper or iron, carbon and a 'flammable gas' were produced, whereas in the presence of pumice stone, ethene and water were observed. In retrospect, catalyst selectivity was demonstrated.

Good insight into the struggle to find an interpretation of observed reaction rates is given by the work Humphry Davy performed at the beginning of the 18th century in the development of a miner's safety lamp. He discovered that coal gas, which contains relatively a lot of methane, burns in the presence of hot platinum and palladium, whereas copper, silver and gold did not exhibit any activity. From the observation that the active metals had to be hot, he concluded that the function of the active metals was heating the reaction mixture. The difference in the behaviour of the two sets of metals was attributed to the difference in their heat capacity and thermal conductivity. Later, it was found that finely dispersed platinum is active already at room temperature. Davy was not right in his explanation, but he discovered that reaction between two gases took place on a metal surface, while this surface did not change chemically.

In 1834, Faraday proposed that in catalysis the reactants have to adsorb simultaneously at the surface, but he did not explain the catalytic mechanism. Berzelius did not give an explanation, but he nicely generalised the observations in a simple description. Later, Ostwald gave the definition that a catalyst does not influence the thermodynamic equilibrium of a reaction, but that the rates are influenced. Berzelius and Faraday proved to be right. Clearly, the 19th century was an important period for catalysis. In a sense, the Nobel Prize of Sabatier for his work on catalytic hydrogenation was the recognition of the importance of this productive period. Sabatier formulated the principle that the reaction intermediates formed at the surface of a catalytic material should have intermediate stability. When too stable, they would not decompose; when too unstable, they would not be formed. This molecular view of the catalytic reaction, not as a single reaction but as a cycle of reaction steps, in which intermediate complexes between a catalyst and a reagent are formed and then decay, was particularly modern. Sabatier's principle is the formulation of the molecular basis of catalytic action and complements Ostwald's physicochemical view.

Table 1.1 gives a survey of the fascinating history of successes in the application of catalysis. The data refer to activities on at least pilot plant scale.

The early industrial catalysis applications were dominated by the development of production processes for organic chemicals, but inorganic chemical production was also important. Early inorganic processes were the production of sulphuric acid, as mentioned above, and the conversion of HCl into Cl2.

The development of the process for the synthesis of NH3 is an enlightening example of a successful R&D project. It was based on the systematic, scientific search for a catalyst that would perform optimally under the envisaged practical conditions. Reading the story of the development of this process is, one century later, still inspiring.

1.2 Ammonia Synthesis

Initially, the source of ammonia was coke oven gas, containing typically 1–5% ammonia, and Chile saltpetre, as the large deposits of NaNO3 in Chile are called. It was recognised as early as the turn of the 20th century that insufficient ammonia was available to cover the agricultural demand. In addition, ammonia was used in increasing amounts to manufacture explosives at the beginning of the First World War. Particularly in Germany, extensive research efforts were made to synthesise ammonia directly from N. Non-catalysed routes were discovered and even commercialised despite their inefficiency, but the breakthrough was the development of a catalytic process.

In 1905, Haber succeeded in producing ammonia catalytically at a temperature of 1293 K and a pressure of 1 bar. The yield was a few percent. He extrapolated his data to lower temperatures and concluded that a temperature of 520 K would be the maximum temperature for a commercial process (at 1 bar). This was the first application of chemical thermodynamics to catalysis and, not surprisingly, accurate thermodynamic data were not available for a broad range of conditions. Haber concluded that the commercial development of a practical process was a hopeless undertaking. Later, in independent work, Nernst concluded that the thermodynamic data of Haber were not correct. On his turn, Haber reinvestigated his data and concluded that a high-pressure route had to be followed. He tried many catalysts and found osmium and uranium to be promising catalysts. He patented a process with a yield of ammonia at 175 atmospheres and 550 °C. The recycle system he developed worked well, see Figure 1.1. In fact, this lay-out is still used nowadays. He approached BASF and they decided on a large development program, in which Bosch was in charge of the scale-up.

The scale-up study was carried out in a systematic, modern way. Three main challenges had to be faced. The feedstock, hydrogen and nitrogen, had to be produced at the lowest cost possible at that stage. A good catalyst had to be developed, the reactor had to be scaled up and the hardware had to be designed and constructed.

Systematic studies were carried out to find a good catalyst. Iron catalysts got special attention because it was known that iron catalyses the decomposition of ammonia, the reverse of the synthesis reaction. It was found that iron alone was only slightly active but its activity could be promoted or worsened by additives. Over 10 000 catalysts were prepared and over 4000 were tested in a kind of high-throughput experimentation program. The catalyst developed at that time is in essence the one still used today.

Regarding the hardware, the major challenge was to develop a reactor that could withstand the harsh reaction conditions (combination of high temperature and high pressure). High-strength carbon steel had to be used because of the high reaction pressures, but this steel was corroded by H2 under those severe reaction conditions. In careful experiments, Bosch discovered that the reason was the decarbonisation of the carbon steel by H2 at high temperature. He designed a reactor that contained an outer wall of high-carbon steel and an internal wall of low carbon steel. The outer wall was protected by cooling it with the feed gas.

Very pure H2 (from water electrolysis) was used in the pilot studies. For a commercial plant this was not practical. What feedstock and what process could enable the development of a commercial process? Up to then, biomass had been the dominant feedstock. In the 19th century, coal became the major raw material. In fact, it was the basis for the industrial revolution. A satisfactory process for the production of H2 was found in a combination of coal gasification and the water–gas shift reaction:C + H2O -> CO + H2CO + H2O -> CO2 + H2

Figure 1.2 places the work of Haber and Bosch in historical perspective. It shows the energy input per amount of product over time. The big step was the Haber–Bosch process, later innovations allowed modest but consistent improvements. Haber received the Nobel Prize for his work on the synthesis of ammonia and later Bosch, together with Bergius, were awarded a Nobel Prize for their achievements in high-pressure technology.

A spin-off of the successful development of the ammonia synthesis was the expertise in high-pressure processes and the availability of synthesis gas that was sufficiently pure for catalytic processes. Processes based on high-pressure hydrogenation reactions, such as the methanol synthesis and the Fischer–Tropsch synthesis, became in principle feasible. In fact, the same team that developed the ammonia synthesis process at BASF also developed the first process for the production of methanol. In the period between 1930 and the Second World War, coal continued to be the main feedstock for the production of chemicals and fuels, although oil and natural gas were playing an increasingly important role, in particular in the U.S.

1.3 Coal Utilisation

Germany was the Walhalla of coal utilisation processes. A major application of coal was the production of the coke needed in large-scale blast furnace processes. The production of coke was a mild pyrolysis process and, besides coke, large quantities of cracking products were produced. Acetylene was a main component and it was seen as a valuable base chemical, for instance, for the production of ethene and vinylchloride. Parallel to the emergence of a synthesis gas based process industry, the high-pressure catalytic hydrogenation of coal was attempted. Not surprisingly, catalyst deactivation was a major challenge. Sulphur appeared to be responsible in many cases. The solution was found in two-stage processing. First, a liquid phase hydrogenation was carried out in a slurry of coal particles (oil produced from coal) with a highly dispersed catalyst. In the second stage, conventional catalyst hydrogenation was carried out in a fixed bed reactor. As early as 1924, it was known that sulphides of Mo, W, Co and Fe were suitable catalysts not poisoned by the heteroatoms (S, N, O) in the feedstock. Much later, during the development of hydrotreating processes in the oil refinery industry, the same catalysts were used. Thus, chemical plants using coal as raw material thrived with a wealth of catalytic processes, in particular in Germany. This work can be considered the origin of catalytic reaction and reactor engineering as we now know it.

1.4 The Oil and Natural Gas Era

Particularly in the U.S., and besides coal, oil and natural gas played a significant role as early as the 1920s. An intense debate arose about what the best option was, coal or oil? From an engineering point of view, oil is preferred because processing liquids (and gases) is much easier than working with solids. However, compared to coal, crude oil is very unreactive, in particular the paraffin fraction. The situation changed when thermal and later catalytic cracking processes were developed.

1.4.1 Catalytic Processes Related to Oil Refinery

In 1930–1960, an impressive number of petroleum-based catalytic processes were developed. The major drive came from the rapidly expanding market for transport liquids with satisfactory properties. For instance, gasoline with high octane numbers was in demand. Catalytic cracking shifted the product spectrum of oil refinery towards the desired boiling point range. It is striking that, in catalytic cracking, process and catalyst development was carried out in such close harmony. Initially, AlCl3 solutions were used, leading to enormous technical and environmental problems of corrosion and pollution. Subsequently, solid catalysts were used in fixed beds and later in fluidised beds. The discovery of zeolites and their high activity enabled the use of riser reactor technology. This cracking technology, referred to as FCC (Fluid Catalytic Cracking), has had an enormous impact.

Although straight-run oil fractions may be in the desired boiling point range for gasoline application, their characteristics do not allow their use in practice. The octane number is too low and exhaust emissions are unacceptable, in particular those of acid rain components. The octane number can be increased by 'catalytic reforming' (major reactions occurring are isomerisation and dehydrogenation to aromatics) catalysed by Pt. Since this catalyst is poisoned by sulphur, a large industry has evolved producing hydrodesulphurisation catalysts. A fortunate side effect of the fact that the gasoline produced is essentially sulphur-free is that an unprecedented reduction in emissions of (gasoline utilising) cars could be realised: catalytic converters were quickly developed in which all of the important emissions of gasoline powered cars were eliminated (CO, NOx and hydrocarbons) to a large extent. At present, it is recognised that diesel is very attractive as automotive fuel. Processes are being developed to increase the production of diesel in refinery (hydrocracking), in combination with tailored hydrodesulphurisation processes.

Natural gas deserves special attention. In steam reforming of natural gas, the synthesis gas produced is very pure, making it an excellent feedstock for catalytic processes. Because of its high purity, synthesis gas based on methane reforming has excellent quality as raw material for catalytic processes. A large variety of bulk chemicals are produced catalytically from syngas, examples being the ammonia and methanol processes mentioned above. In the 1960s, at Imperial Chemical Industries (ICI), a breakthrough finding was the development of highly active catalysts leading to the so-called low-pressure process. This is a good example of the often encountered situation that a new catalyst leads to completely new technology. The route to low-cost and rather pure syngas is also the basis for 'gas-to-liquid' technology, referred to as the Fischer–Tropsch synthesis.

(Continues...)

Excerpted from Contemporary Catalysis by Paul C. J. Kamer, Dieter Vogt, Joris W. Thybaut. Copyright © 2017 The Royal Society of Chemistry. Excerpted by permission of The Royal Society of Chemistry.
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Edition details

• Publisher: Royal Society of Chemistry
• Publication date: 2017
• Language: English
• ISBN 10: 1849739900
• ISBN 13: 9781849739900
• Binding: Hardcover
• Edition number: 1
• Number of pages: 896
• Editor: Kamer Paul C J, Vogt Dieter, Thybaut Joris